AU671257B2 - Catalyst treatment - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Description
OPI DATE 11/02/93 A0JP DATE 08/04/93 APPLN. ID 21531/92111111 PCT NUMBER PCT/GB92/01141 1I11I1111I111III1111II 111111111iii111111 AU9221531 jj,~£LII~fA CiAI Lktitt~~i a. a a~ ~r) (51) International Patent Classification 5 International Publication Number: WO 93/00993 BOWJ 37/16, 23/74, C07C 1/04 Al (43) International Publication Date: 2-1 January 1993 (21.01.93) (21) International Application Number: P)CT/G1392/Ol 141 (74) Agent: WILSON, Michael, John; 1l1P International Limited, Patents Agreements D~ivision, Chertsey Road, Sun- (22) International Filing Date: 24 June 1992 (24.06.92) bury-on-Thames, Middlesex, TW16 7LN (GB).
Priority data: (81) Designated States: AU, CA, Fl, JP, NO, European patent 911l4314.9 2 July 1991 (02.07,9 1) GB (AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LU, MIC, NL, SE).
(71) Applicant: THE BRITISH PETROLEUM COMPANY P.L.C. [GB/GB]; Britannic House, I Finsbury Circus, Published London EC2M 7BA nW internaiional seairch report.
(72) Inventors: NAY, Barry 29 Greenham Walk, Woking, Surrey GU21 3HB SMITH, Mark, Royston 10 Camilla Close, Sunbury-on-Thames, Middlesex TWI6 7PZ (GB1). TELFORD, Clive, D~avid 145 Cavendish Meads, Sunninghill, Berks, SL5 9TG (GB).
(54)Title: CATALYST TREATMENT (57) Abstract A cobalt catalyst for use in the Fischer Tropsch reaction of synthesis gas to form hydrocarbons is activated or regenerated by treatment of a cobalt containing catalyst with a gas containing carbon monoxide, said gas containing less than 30 9o v hydrogen. The catalyst obtained has increased activity and greater selectivity towards producing CS hydrocarbons.
la CATALYST TREATMENT The present invention relates to a process for treating a cobalt containing catalyst which is suitable for use in a Fischer Tropsch process, to a treated cobalt containing catalyst produced by such process, to a process for producing hydrocarbons in the presence of such catalyst, to hydrocarbons produced by such process, and to a method for increasing the activity and/or selectivity of a cobalt containing Fischer Tropsch catalyst towards C 5 hydrocarbons.
The Fischer Tropsch process for the conversion of synthesis gas into hydrocarbons over an iron or cobalt containing catalyst is very well known. Various different methods of either activating a fresh catalyst or regenerating a used catalyst have been proposed. Most preferred is the treatment of the catalyst with hydrogen especially alone, but the use of hydrogen mixed with a minor proportion of carbon monoxide has also been described (see eg. USP 4626552). DE 977498 describes the pretreatment with a carbon monoxide containing gas of a catalyst of Group VIII of the Periodic Table, especially an iron one, for the hydrogenation of carbon monoxide.
We have now found a special treatment programme for cobalt-containing catalysts which can be incorporated into a Fischer Tropsch reaction to increase the catalyst activity and/or increase the selectivity for producing
C
5 hydrocarbons.
Accordingly, the present invention provides a process for treating a cobalt containing catalyst to produce a treated cobalt containing catalyst wherein: the cobalt containing catalyst is suitable for use in a Fischer Tropsch process; a major proportion of the cobalt in the cobalt containing catalyst is present in an oxide form; and at most, a minor proportion of the cobalt in the cobalt containing catalyst is present is cobalt metal, 0
'J
SI 1535EZ/700 Ib the process comprising the step of contacting the cobalt containing catalyst with a gas containing carbon monoxide at a temperature of 100-500 0 C, wherein the gas containing carbon monoxide contains less than 30% by volume of hydrogen.
The temperature of 100-500 0 C is preferably 200 to 350 0 C and, more preferably, is a temperature above the mean temperature in the subsequent Fischer Tropsch process, preferably at least 10 0 C above said temperature such as 10-60 0 C or S:1 155F77nn WO 93/00993 PCT/GB92/01141 2 \e vxa especially 25-55'C above; most preferred aLova temperaLures. are 220-260°C especially around 250'C.
The gas used may be composed substantially entirely of carbon monoxide or of carbon monoxide containing only small amounts of other materials e.g. up to 10% v/v such as 1-10%, but the gas may if desired contain up to 95 e.g. 10-95% for example up to 60 %v e.g. 20-50%v based on the total volume of the gas), of other components such as nitrogen or argon which are inert. These gases may act as inert carrier gases. The gas comprising carbon monoxide is preferably substantially free from hydrogen. If it does contain some hydrogen, it is essential that the hydrogen content of the gas is less than 30, especially less than 20, preferably less than and most preferably less than 5, %v based on the volume of carbon monoxide; the gas may contain 1-30% or 5-20% v/v hydrogen (based on carbon monoxide). The treatment may be carried out at any desired pressure e.g. 50-10OOkPa (0.5-10 bar) with, atmospheric pressure being preferred. The treatment time is not crucial, the optimum treatment time depending of course on the precise conditions such as the temperature and flow rate of the gas. Suitable treatment times are for example at least 10 minutes, preferably from 1 to 12 hours.
The cobalt in the cobalt containing catalyst before said treatment is usally present at least partially in an oxidic form e.g. as free cobalt oxide or a mixed oxide with an oxidic support; the cobalt with catalyst before treatment may be in a major proportion in the oxide form with at most a minor proportion of cobalt metal; but especially, with a fresh catalyst may be substantially in the oxidic form. Under the preferred treatment conditions, the cobalt containing catalyst interacts with the carbon monoxide but avoids significant deposition, especially substantially any deposition of refractory carbon residues; thus conditions of 230-270°C for at atmospheric pressure may be used, higher temperatures requiring shorter times. The interaction is believed to be a reduction of the oxidic cobalt catalyst; in particular to reduce the cobalt to give a product in which a majority of the cobalt is present as cobalt metal e.g. 51-99% such as 80-90% (as determined by hydrogen analysis or r s WO 93/00993 PCr/GB92/01141 3 carbon dioxide analysis on the gaseous effluent from the treatment), and a minority of the cobalt is present as a cobalt oxide e.g. 1-49% such as 10-20%.
This treatment can be used as an activation for a fresh cobalt-containing catalyst, or it can be used as part of a regeneration sequence for a cobalt containing catalyst which has already been used in a Fischer-Tropsch reaction. In either case, the treatment leads to improved performance in a subsequent Fischer-Tropsch reaction. This improvement is not seen with conventional activation or regeneration treatments such as treatment at elevated temperature with hydrogen. Thus in a further embodiment, the present invention provides a method of increasing the activity and/or selectivity of a cobalt containing Fischer Tropsch catalyst towards C 5 hydrocarbons, in which the catalyst has been treated by the process of the invention, and also provides the use of said treated catalyst for said purpose.
Prior to treatment with carbon monoxide, the cobalt-containing catalyst may be given a pre-treatment by treating at elevated temperature with a gas containing molecular oxygen, such as air.
This pretreatment is especially useful with used Fischer Tropsch catalysts which can be oxidized by it to produce the cobalt containing catalyst in an oxidic form. The elevated temperature for this pre-treatment is usually in the range of from 200 to 600°C, especially 300 to 500°C or 280-550'C. The treatment may be carried out at any desired pressure, atmospheric pressure being preferred.
The optimum treatment time will depend upon the history of the catalyst, on the oxygen content of the gas used and on the treatment conditions. The treatment time should in general be of sufficient length to remove any carbonaceous residues present on the catalyst especially one for regeneration. Treatment times of at least minutes, preferably from I to 48 hours, are preferred.
A well known problem with Fischer-Tropsch reactions is the start-up procedure. To obtain stable conditions, a very long start-up period may be required. Temperature instabilities can lead to major difficulties. US 4626552, describing these problems, WO 93/00993 PCT/GB92/01141 4 states that it requires from 8 to 18 days to bring a Fischer-Tropsch reactor on stream, and discusses the problem of temperature runaway, caused by excessive heat and/or pressure during start-up. The present invention leads to a way of avoiding these problems. Thus, in a further embodiment, the present invention provides a process for the conversion of synthesis gas into hydrocarbons which comprises passing synthesis gas over a cobalt-containing catalyst under Fischer-Tropsch conditions; characterised in that the process comprises the following steps in succession: i) treating the cobalt-containing catalyst at elevated temperature with a gas containing carbon monoxide, said gas containing less than 30%v of hydrogen based on the volume of carbon monoxide; ii) passing synthesis gas over the cobalt-containing catalyst so treated at a temperature which is at least 10*C higher than the maximum temperature attained during the subsequent step carried out under said Fischer-Tropsch conditions; and iii) passing synthesis gas over the cobalt-containing catalyst under said Fischer-Tropsch conditions. Benefits of step (ii) can be shortened start-up time to uniform Fischer Tropsch operation, a higher activity catalyst and better selectivity to C 5 hydrocarbons.
Following the treatment step i) of the process according to the invention, the cobalt-containing catalyst is subjected to a start-up procedure, step ii), which involves passing synthesis gas over the cobalt-containing catalyst at a temperature which is at least higher, preferably at least 20°C higher such as 10-150°C especially 50-110°C higher than the maximum temperature attained during the subsequent Fischer-Tropsch reaction, step iii). Suitable temperatures for step (ii) are in the range of from 220 to 330°C e.g. 230 to 300'C, especially 240 to 300*C. The pressure is preferably in the range of from 100 to 10,000 kPa (to 100 bar), more preferably 100 to 5,000 kPa (to 50 bar), especially 1,000 to 5,000 kPa (10 to 50 bar).
During step ii), it may be observed that an exotherm moves through the entire catalyst bed, especially with a fixed bed. The optimum period of time required for the step is that time required WO 93/00993 PCI/GB92/01141 for the exotherm to move right through the bed. Once this has happened, it is desirable to end start-up step ii). The optimum duration of step ii) will depend on the flow ratio of carbon monoxide. Preferably the duration of step ii) is greater than minutes, for example 0.5 to 12 hours.
The start-up step ii) is unusual in Fischer-Tropsch technology,where conventional wisdom is that high temperatures and pressures must be avoided during start-up in order to avoid temperature runaway and damage to the catalyst.
Following the start-up step ii), the desired Fischer-Tropsch reaction is carried out in step iii). Fischer-Tropsch conditions are well known to those skilled in the art. Preferably, the temperature is in the range of from 150 to 300'C, especially 180 to 240°C, most preferably 180 to 230*C with a mean temperature of 190-235"C especially 195-220'C, and the pressure is in the range of from 100 to 10,000 kPa (to 100 bar), more preferably 100 to 5000 kPa (to 50 bar), especially 1,000 to 5,000 kPa (10 to 50 bar).
Preferably there is no interruption in the synthesis gas feed between steps ii) and iii), but if desired, the catalyst can be stored after step ii) is complete and used subsequently in step iii) when required. After step the temperature can be reduced to that required for the Fischer Tropsch process, but preferably the temperature is reduced to a temperature below 200°C especially to 150-190*C before being raised again to the mean Fischer Tropsch operating temperature.
Synthesis gas is a mixture of hydrogen and carbon monoxide.
The relative quantities of the two components may vary, but the molar ratio of hydrogen to carbon monoxide is usually in the range of from 1:1 to 3:1. Preferably the molar ratio of hydrogen to carbon monoxide is in the range of from 1.8:1 to 2.2:1. The feedstock gas used in step ii) or step iii) may if desired contain other components, for example nitrogen, paraffins, olefins and/or carbon dioxide. Nitrogen may be present to act as a carrier gas or co-feed, and if so is preferably present in an amount of less than 40%v, for example from 10 to 40%v. Other components are preferably WO 93/00993 PCT/GB92/01141 6 present in minor amounts, typically less than 20%, especially less than 15, %v.
The cobalt catalyst used in the present invention preferably comprises cobalt on a support. Very many suitable supports may be used, for example silica, alumina, titania, ceria, zirconia or zinc oxide. The support may itrelf have some catalytic activity.
Preferably the catalyst contains from 2 to 35%w, especially from to 25%w, of cobalt. Alternatively, the cobalt catalyst may be used without a support. In this case, the catalyst is often prepared in the form of cobalt oxide. Active metal catalytic components or promoters may be present as well as cobalt if desired.
The process of the invention may be performed in a fluid bed or a fixed bed or in a slurry in a liquid e.g. of liquid hydrocarbon product. The treatment process of the invention with carbon monoxide e.g. step above may be performed in the same or a different reactor from that of the start-up or Fischer Tropsch step (ii) or (iii) above).
The following Examples 1 and 3-5 illustrate the invention.
Example 1 Catalyst Preparation A catalyst containing 10%wt cobalt on zinc oxide was prepared as follows.
Deionised water (3.35 kg) was added to ZnO (10.00 kg) with mixing. After 5 minutes Co(N0 3 2 .6H 2 0 (5.55 kg) dissolved in deionised water (4.15 kg) was added with stirring using a Z-blade mixer. After mixing the water was removed by drying in air at 120°C for 15 hours to leave a product, which was then further heated to 500°C (at a rate of 50'C/h) and then maintained at 500°C for a further 5 hours. The calcined catalyst obtained (9.23 kg) was lubricated with 2 wt% stearic acid and formed into tablets 3.175mm diameter x 2 mm) which were subsequently heated to 500°C (at a rate of 100*C/h) and then maintained at 500°C for 1 hour in air.
The tablets were cooled to room temperature in air, ground and sieved to 250-500pm mesh size.
WO 93/00993 PCT/GB92/01141 7 Example 2 (Comparative) In situ H 2 Pretreatment g (250-500pm) of the catalyst prepared in Example 1 were charged into a microreactor. Hydrogen was introduced at a GHSV (gas hourly space velocity) of 1000 h-l and the temperature raised from to 320*C at 10'C min 1 The temperature was held at 320°C for and then the reactor cooled at 10°C min I to room temperature.
Example 3 3h Carbon Monoxide in situ Reduction 10 g (250-500pm) of the catalyst prepared in Example I were charged into a microreactor. Nitrogen was introduced at GHSV=1000 h 1 and the temperature raised from 30°C to 250°C at 10*C min 1 Then the nitrogen was switched off and carbon monoxide introduced at GHSV=900 h-1 for 3h. The reactor was then cooled at 10*C min I to Example 4 In situ Air Pretreatment Followed by 3h Carbon Monoxide Reduction g (250-500pm) of the catalyst prepared in Example 1 were charged into a microreactor. Air was introduced at GHSV=6000 h-l and the temperature raised from 30 to 500"C at 10'C min-1. The temperature was held at 500*C for 44 h and then cooled to 250*C.
Carbon monoxide was introduced at GHSV=900 h-1 and after 3 h at 250"C the reactor was cooled at 10*C min I to Catalysts from Examples 2, 3 and 4 were all tested using the following procedure.
Reaction Start-up and Fischer-Tropsch Reaction Following on from Examples 2, 3 and 4 the microreactor at a temperature below 30°C, was purged with a gas mixture containing nitrogen, and also hydrogen and carbon monoxide in a molar ratio of 2.07:1. The pressure was then increased to 3000 KPa bar) and the GHSV of the gas mixture passed adjusted to 1250 h 1 The applied temperature was raised to 250°C at 2°C min-1, and then held for 1 h at 250°C. The bed temperature was then decreased to 180°C and then slowly increased until about 80% carbon monoxide conversion was achieved. Conversion was measured from gas WO 93/00993 PCT/GB92/0 1141 8 chromatography analysis of exit gas using N 2 marker. The results are shown in Tables 1 to 4. Productivity C5+ is the total number of grams of C 5 product formed per litre of catalyst per hour.
Because the tests were arranged to run at constant conversion, the bed temperature observed gives a measure of the activity of the catalyst being tested. Thus, a more active catalyst can achieve an carbon monoxide conversion at a lower temperature than a less active catalyst.
Comparison of Tables 1 and 2 shows that the catalyst treated with carbon monoxide according to the invention shows higher initial activity than the catalyst given a conventional hydrogen treatment.
In addition, production of undesired C 1 products is considerably lower and production of the desired C5+ products is considerably higher.
Table 3 shows the additional benefits of an air treatment followed by a carbon monoxide treatment: the productivity is considerably increased.
WO 93/00993 PCT/GB92/01141 9 TABLE 1 Catalyst Treatment According to Example 2 (Comparative) Hours Mean Bed Conversion Carbon Molar Selectivity Bed Prod on Temp Stream CO H 2
CH
4
CO
2
C
2
C
2
+C
4 C5+ C 2 54 214 73.9 82.8 8.0 0.5 1.7 9.0 80.9 91.5 125 149 216 74.2 80.1 7.8 1.4 1.3 6.9 82.6 90.8 128 TABLE 2 Catalyst Treated According to Example 3 Hours Mean Bed Conversion Carbon Molar Selectivity Product-1 on Temp ivity Stream CO H 2
CH
4
CO
2
C
2
C
2
C
4 C5+ C2+ C 5 26 202 78.7 82.2 5.9 1.1 0.6 3.6 88.8 93.0 145 77 209 83.9 90.4 7.1 2.4 0.5 2.2 87.8 90.6 153 149 210 86.4 88.5 7.0 2.2 0.5 2.2 88.0 90.8 158 TABLE 3 Catalyst Treated According to Example 4 Hours Mean Bed Conversion Carbon Molar Selectivity Producton Temp ivity Stream CO H 2
CH
4
CO
2
C
2
C
2
+C
4 C5+ C2+ C 5 26 204 90.4 92.5 7.6 1.5 0.7 3.4 86.8 90.9 163 94 205 84.2 87.1 5.5 0.8 0.5 2.6 90.6 93.7 159 144 205 79.8 80.6 6.2 0.8 0.6 3.4 89.0 93.0 148 WO 93/00993 PCT/GB92/011.41 Example A 10% cobalt on zinc oxide catalyst was prepared by the general method of Example 1. One portion of the catalyst was treated with air for 6 hours at 500°C followed by hydrogen for 9 hours at 320°C, while a second portion was treated with air for 50 hours at 500°C followed by carbon monoxide for 3 hours at 250*C. Both catalysts were then tested by the method described above. The results are given in Table 4 below, and show the clear advantages of the treatment involving carbon monoxide.
TABLE 4 Catalyst Hours Mean Bed CO Carbon Molar Selectivity Treatment on Temp Conversion Stream CH 4
CO
2 Air/H 2 214 214 87 7.5 2.5 76.8 (Comparative) Air/CO 213 212 87 4.6 1.9 91.0 Example 6 An Unsupported Catalyst Preparation Ammonium bicarbonate (1145 g) was dissolved in deionised water (10.4 dm 3 and 500 cm 3 of the solution added to a continuous precipitation cup. In a second vessel cobaltous nitrate (450.6 g) was dissolved in deionised water (2.8 dm3). The two solutions were pumped simultaneously into the solution already in the precipitation cup at such a rate as to ensure complete precipitation of cobalt oxide (rapid agitation was required within the precipitation cup).
The precipitate was constantly being removed via a weir and filtered on a Buchner funnel. The complete precipitation process was completed in 2 hours. The filter cake was dried overnight in air at WO 93/00993 IPC/GB92/0 141 11 150'C and then in air at 350*C for 6hr to give 114.4 g of Co 3 0 4 Test A portion of the above catalyst was treated with hydrogen as described in Example 2 and tested using the reaction start-up procedure described earlier. The results are shown in the first row of Table 5. The catalyst so tested was then treated with 1% 02/99%
N
2 at 500*C for 23 hours. The temperature was then reduced to 250'C and the catalyst treated with CO for 3 hours. The catalyst was again tested using the same reaction start-up procedure. The much improved results are shown in the secrnd row of Table TABLE Catalyst Hours Mean Bed CO Carbon Molar Selectivity Treatment on Temp Conversion Stream CH 4
CO
2
H
2 25 257 33 37.4 1.3 28 (Comparative) 1% 0 2 /CO 25 231 69 14.1 1.5 105
Claims (14)
1. A process for treating a cobalt containing catalyst to produce a treated cobalt containing catalyst wherein: the cobalt containing catalyst is suitable for use in a Fischer Tropsch process; a major proportion of the cobalt in the cobalt containing catalyst is present in an oxide form; and at most, a minor proportion of the cobalt in the cobalt containing catalyst is present is cobalt metal, the process comprising the step of contacting the cobalt containing catalyst with a gas containing carbon monoxide at a temperature of 300-500 0 C, wherein the gas containing carbon monoxide contains less than 30% by volume of hydrogen.
2. A process as claimed in claim 1 wherein the cobalt in the cobalt containing catalyst is substantially in an oxide form.
3. A process as claimed in claim 1 or claim 2 wherein the cobalt containing catalyst comprises cobalt on a support.
4. A process as claimed in any one of the preceding claims wherein the gas containing carbon' monoxide is substantially free of hydrogen.
5. A process as claimed in any one of the preceding claims wherein the cobalt containing catalyst is contacted with the gas containing carbon monoxide at a temperature of 200-350 0 C.
6. A process as claimed in claim 5 wherein the cobalt containing catalyst is contacted with the gas containing carbon monoxide at a temperature of 230-260 0 C.
7. A process as claimed in any one of the preceding claims wherein the cobalt containing catalyst is obtained by contacting a catalyst containing cobalt with a gas containing molecular oxygen at elevated temperature.
8. A process as claimed in claim 7 wherein the catalyst containing cobalt is contacted with the gas S:11535EZ/700 13 containing molecular oxygen at a temperature of 380- 600 0 C.
9. A process for treating a cobalt containing catalyst to produce a treated cobalt containing catalyst, the process being substantially as herein described with reference to any non-comparative Example.
A treated cobalt containing catalyst produced by a process as claimed in any one of the preceding claims.
11. A process for producing hydrocarbons from synthesis gas, the process comprising the step of treating the synthesis gas under Fischer Tropsch conditions in the presence of a treated cobalt containing catalyst as claimed in claim
12. A process as claimed in any one of claims 1-9 further comprising the step of passing synthesis gas over the treated cobalt containing catalyst under Fischer Tropsch conditions to form hydrocarb-ns.
13. A process as claimed in claim 12 wherein, prior to passing synthesis gas over the treated cobalt catalyst under Fischer Tropsch conditions, synthesis gas is passed over the treated cobalt containing catalyst at a temperature which is at least 10 0 C higher than the maximum temperature at which synthesis gas is subsequently passed over the treated cobalt containing catalyst under Fischer Tropsch conditions.
14. Hydrocarbons prepared by a process as claimed in S.any one of claims 11-13. A method of increasing the activity and/or selectivity of a cobalt containing F4 her Tropsch catalyst towards C 5 hydrocarbons, the method comprising treating the cobalt containing Fischer Tropsch catalyst by a process as claimed in any one of claims 1-9. DATED this 21st day of June 1996 THE BRITISH PETROLEUM COMPANY PLC By its Patent Attorneys GRIFFITH HACK CO. 'S:11535EZ/700 ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION No. GB SA 9201141 61298 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on The European Patent Office is in no way liable for thesn particulars which are merely given for the purpose of information. 11/09/92 DE-C-977498 None FR-A-i 108326 None BE-A-502597 None INTERNATIONAL SEARCH REPORT International Application No PCT/GB 92/01141 I I I. CLASSIFICATION OF SUBJECT MATTER (f several classification symbols apply, Indicate all) 6 According to international Patent Classification (IPC) or to both National Classification and IPC Int.Cl. 5 B01J37/16; B01J23/74; C07C1/04 I. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols Int.C1. 5 B01J C07C Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched 8 mI. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category Citation of Document, It with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 A DE,C,977 498 KbLBEL) 3 November 1966 1-10 cited in the application see page 1, line 33 page 2, line see page 4; examples 1,2 see claims A FR,A,1 108 326 (RHEINPREUSSEN AG) 11 January 1-10 1956 see the whole document A BE,A,502 597 (RUHRCHEMIE AG) 18 July 1952 1-10 see page 1, line 1 line 11 see page 2, line 36 line 48 see claims a Special categories of cited documents :10 later document published after the international filing date or priority date and not In conflict with the application but document defining the general state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to L' document which may throw doubts on priority claim(s) or Involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the "0 document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 1 11 SEPTEMBER 1992 g1 SEP 1992 International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE LO CONTE C. Farm PCTIISA/210 (secid lhel) (Jamary 1985
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB9114314 | 1991-07-02 | ||
GB919114314A GB9114314D0 (en) | 1991-07-02 | 1991-07-02 | Catalyst treatment for fisher-tropsch process |
PCT/GB1992/001141 WO1993000993A1 (en) | 1991-07-02 | 1992-06-24 | Catalyst treatment |
Publications (2)
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AU2153192A AU2153192A (en) | 1993-02-11 |
AU671257B2 true AU671257B2 (en) | 1996-08-22 |
Family
ID=10697719
Family Applications (1)
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AU21531/92A Ceased AU671257B2 (en) | 1991-07-02 | 1992-06-24 | Catalyst treatment |
Country Status (13)
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US (2) | US5585316A (en) |
EP (1) | EP0593522B1 (en) |
CN (2) | CN1039974C (en) |
AU (1) | AU671257B2 (en) |
CA (1) | CA2112372C (en) |
GB (1) | GB9114314D0 (en) |
GE (1) | GEP19991740B (en) |
MX (1) | MX9203906A (en) |
MY (1) | MY109626A (en) |
NO (1) | NO304177B1 (en) |
UA (1) | UA39925C2 (en) |
WO (1) | WO1993000993A1 (en) |
ZA (1) | ZA924937B (en) |
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- 1992-06-24 UA UA94005352A patent/UA39925C2/en unknown
- 1992-06-24 AU AU21531/92A patent/AU671257B2/en not_active Ceased
- 1992-06-24 WO PCT/GB1992/001141 patent/WO1993000993A1/en active IP Right Grant
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- 1992-07-02 ZA ZA924937A patent/ZA924937B/en unknown
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CA2112372A1 (en) | 1993-01-21 |
US5585316A (en) | 1996-12-17 |
CA2112372C (en) | 2002-10-08 |
CN1039974C (en) | 1998-09-30 |
NO304177B1 (en) | 1998-11-09 |
NO934880L (en) | 1994-02-22 |
CN1070594A (en) | 1993-04-07 |
MY109626A (en) | 1997-03-31 |
CN1064660C (en) | 2001-04-18 |
GEP19991740B (en) | 1999-09-10 |
US5728918A (en) | 1998-03-17 |
EP0593522B1 (en) | 1997-11-05 |
CN1176243A (en) | 1998-03-18 |
WO1993000993A1 (en) | 1993-01-21 |
NO934880D0 (en) | 1993-12-29 |
MX9203906A (en) | 1993-04-01 |
ZA924937B (en) | 1994-05-04 |
GB9114314D0 (en) | 1991-08-21 |
UA39925C2 (en) | 2001-07-16 |
AU2153192A (en) | 1993-02-11 |
EP0593522A1 (en) | 1994-04-27 |
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